N&#39;-acyl-n&#39;-hydrocarbon-n-tertiary aminoloweralkyl-asparagines



United States Patent Ofi" 3,337,548 Patented Aug. 22, 1967 3,337,548 N'-ACYL-N-HYDROCARBON-N-TERTIARY AMINOLOWERALKYL-ASPARAGINES Gregoire Kalopissis and Andr Viout, Paris, and Guy Vanlerberghe, Mitry-Mory, France, assignors to So ciete anonyme dite: LOreal, a corporation of France No Drawing. Filed Feb. 26, 1964, Ser. No. 347,397 Claims priority, application France, Mar. 1, 1963, 926,440, Patent 1,419,574 15 Claims. (Cl. 260-2472) This invention relates to surface-active compounds of amphoteric character and processes for their preparation.

This is an improvement over the invention disclosed in US. application Ser. No. 256,142, filed Feb. 4, 1963, now abandoned in favor of continuation-in-part application Ser. No. 487,084, filed Sept. 13, 1965, in the names of Grgoire Kalopissis and Andr Viout which describes asparagine derivatives having surface active activity and which can be used in shampoos which conforms to the formula:

and their acid addition and sodium, potassium and ammonium salts, in which is selected from the group consisting of dilower alkylamino, R and R having 1 to 4 carbon atoms morpholino or piperidino, n is 2 to 5, preferably 2 or 3, and R is an aliphatic hydrocarbon residue containing to 18 carbon atoms.

It has now been found according to the present invention that related compounds containing additional fatty amine and carboxylic acid groups provide products which are particularly useful in the hair shampoo field.

The compounds of the present invention are compounds of the formula:

and their acid addition salts, in which is selected from the group consisting of dilower alkylamino, morpholino or piperidino, n is 2 to 5, and R and R are the same or different aliphatic hydrocarbon residues containing 10 to 18 carbon atoms each.

These new products have the following advantages. They possess good surface-active properties so that they can be used as hair shampoos, over a very wide pH range,

for example from 3 to 10. In addition to their good detergent properties, they have the advantage of preventing the accumulation of electrostatic charges, impart a soft handle to the hair and permit ready combing. They are very well tolerated by the mucous membrane of the eye.

They possess very good thickening power and consequently can be employed as additives to aqueous solutions of other surface-active substances of cationic, anionic or nonionic character. The last advantage is very appreciable in practice owing to the fact that the thickening is effected by substances which can themselves 'be used alone as shampoos, in contrast to known products, which are not both thickening and washing agents.

The process for the preparation of the new compounds according to the invention consists in condensing maleic anhydride with the asparagine derivatives, described in the aforesaid application, of the Formula I, and thereafter adding a fatty amine of formula RNH to the double bond of the resultant product.

As particularly suitable fatty amines, there may be mentioned: decylamine and dodecylamine, and also the amines derived from the fatty acids of copra and tallow.

The invention includes within its scope washing and cleaning compositions, in particular shampoos having a pH of from 3 to 8 which contains one or more compounds of the Formula II.

These compositions may be in the form of aqueous solutions and their pH may be acid, neutral or alkaline. The compounds of Formula II function either as cationic or anionic agents, depending upon the pH.

As already stated, aqueous solutions of the compounds of Formula II are innocuous to the mucous membrane of the eye. This has been shown by tests carried out by applicants, summarized in the following tables.

TABLE I Application of a solution of:

R =R =alkyl residues from copra fatty acids at a concentration of 0.05 m. (M.W.=816) R =R'-=alkyl residues from copra fatty acids at a concentration of 0.05 m. (M.W.=703) 3 TABLE III Application of a solution of:

CHgCO-NH(CHz)a-N R NCH-COONa C2H5 R :R'=alkyl residues from copra fatty acids at a concentration of 0.05 m. (M.W.=744) Observation 24 hours after application Observation 7 days pH after application TABLE IV Application of a solution of:

Rabbits WwNHPWMD- OOCOQQOC ODQOOOOO R =R'=alky1 residues from tallow fatty acids at a concentration of 0.05 m. (M.W.=882) Application of a solution of:

R =R'=alkyl residues from tallow fatty acids at a concentration of 0.05 m. (M.W.=9l0) 4. TABLE VI Application of a solution of:

CzHs

CHzCONH(CHz)a R3-NCHC o ONa C211 ]OCH2CH-COONa R-NH R =alkyl residue from tallow fatty acids and R=alkyl residue from copra fatty acids in a concentration of 0.05 m. (M.W.=834) Observation Observation pH Rabbits 24 hours after 7 days after application application 1 0 8 2 0 p 3 3 0 0 4 0 0 1 0 8 2 O pH7and pH 8.... 3 0 0 4 0 0 TABLE VII A plication of a solution of:

C H2 0 Hz CH2C ONH(CH2)z-N O R NCHOHC 0 OK GHzCHi R =R"=a1kyl residues from copra fatty acids in a concentration of 0.05 m. (M.W.=790) Observation 24 Observation7 days pH Rabbits hours after after application application 1 gecovereg 2 ecovere p 3 3 4 1 Recovered t 2 R 0 d ecovere pH 7 3 1 Recovered 4 0 0 1 1 R 0 d 2 ecovere pH 8 3 4 2 weak Recovered The symbols employed in these tables have the follow ing meanings:

O=no irritation;

1=irritation of the bulbar or palpebral conjunctiva;

2=irritation of both the bulbar and palpcbral conjunctivae;

3:2 plus Watering (recovery);

4:3 plus nonpurulent secretion (recovery);

5:4 plus purulent secretion, closing of the eyelids, roughened cornea with possible insensitivity (recovery slow, but possible);

6:5 plus attack on the palpebral edges and even on the skin;

numbers 1 to 6 may be followed by l to 5 crosses in accordance with the intensity of the action; since the corneal lesions are of two types, the numbers corresponding to the strongest action may also be followed by (a),

Which corresponds to a loss of lustre (roughened cornea),

or (b), which corresponds to the more or less complete destruction of the corneal epithelium with more or less extensive ulceration and loss of corneal sensitivity. The cornea may be attacked in cases 5 and 6 either by the determine the point of amine employed, owing to the fact that the final product contains only 24% thereof.

-product itself or by the pathological conjunctival secretion produced by the product. Loss of corneal sensitivity facilitates the production of ulceration.

It is clearly apparent from the tests summarized in the foregoing tables that the products of the invention do not attack the cornea, as do many known cationic, anionic and nonionic products. By way of comparison, it is to be noted that the application of solutions of the same concentration by weight and with the same pH, of cetyltrimethylammonium bromide to the eye of rabbits gives lesions which would be placed between 3 and 6 in the foregoing scale.

The new compounds may be employed in various fields and notably in the cosmetic field. As already stated, they may be employed With advantage for thickening hair washing compositions.

The following examples illustrate the preparation of the new chemical compounds, and also the compositions of the invention.

Examples of the preparation of the new compounds:

Example 1 Preparation of the disodium partyl)-asparagine of the formula:

salt of N -(alkyl, as-

mula

RaNH-C 11-0 ONa 0211 in which R is an alkyl residue derived from the fatty acids of copra, in 300 cc. of tert.butyl alcohol, is added, at a temperature of 50 C. with stirring, 1 mol. of maleic anhydride. The whole is maintained at this temperature for about 1 hour. The temperature is then allowed to return to normal, and neutralisation is effected by means of concentrated aqueous sodium hydroxide solution. 1 mol. of copra fatty amine is thereafter added and the mixture is heated for 12 hours at 65 C. with stirring. The solution is evaporated in vacuo. The product obtained 'is substantially colorless and can be reduced to flakes by grinding. The progress of the reaction is observed with the usual analytical determinations carried out both on the intermediate and final products. It is thus possible to disappearance of the primary partyl)-asparagine of the formula:

in which R and R represent alkyl residues derived from -'the fatty acids of tallow.

The procedure of Example 1 is followed, but the amines derived from the fatty acids of tallow are employed instead of copra amines. The desired product is obtained in the form of a solid mass.

in which R is an alkyl residue derived from the fatty acids of tallow. The product obtained takes the form of a solid mass which can be reduced to flakes by crushing.

Example 4 Preparation of the disodium salt of N -(alkyl, aspartyl)-asparagine of the formula:

CH OHrCONH(CHz)a-N R3NGH-COON-a O-CHz-CHCOONa represent the alkyl residues derived in which R and R from the fatty acids of copra.

By proceeding in the same way as in Example 1, but starting with the sodium salt of N-(N',N'-dimethylarninopropy1)-N -(alkyl)asparagine of the formula:

in which R represents an alkyl residue derived from the fatty acids of copra, a substantially colorless solid prodnot is obtained.

Example 5 of N -(alky1, asparin which R and R represent alkyl residues derived from the fatty acids of tallow.

The same procedure is followed as in Example 4, but

arnines derived from the fatty acids of tallow are em- ,ployed instead of copra fatty amines. After evaporation of the water and the alcohol, the desired product is obtained in solid form. It can be reduced to flakes by grinding.

Example 6 of N (alkyl, aspar- 7 in which R, and R represent alkyl residues derived from the fatty acids of copra.

The same procedure is followed as in Example 1, but starting with the sodium salt of N-(N,N-diethylaminoethyl)-N -(alkyl)asparagine of the formula:

0112- ONH (CH2)2N R NHCHOOONa 0 11 in which R represents an alkyl residue derived from the fatty acids of copra.

The desired product is obtained by proceeding as in Example 1.

Example 7 Preparation of the dipotassium salt of N -(alkyl, aspartyl)-asparagine of the formula:

COGHZCHC 0 0K RNH in which R and R represent alkyl residues derived from the fatty acids of copra.

The same procedure is adopted as in Example 1 above, but starting with the potassium salt of N-(N-morpholinoethyl)-N -(alkyl) asparagine of the formula:

CHQCHQ C|1HC O-NH(CH )zN R NHCH-O 0 OK CHZCHQ in which R represents an alkyl residue derived from the fatty acids of copra. The desired product is obtained in the form of a solid mass which can be reduced to flakes by grinding.

Examples of the application of the new compounds:

Example 8 There is prepared an aqueous solution containing:

Disodium salt of N -[alkyl(copra)aspartyl] N -[alkyl(copra)] N (N,N diethylaminopropyhasparagine 7 g. N [alkyl(copra)] N (N,N' diethylaminopropyl)asparagine 6 g. Lactic acid to pH 6. Water to 100 cc.

This solution gives a viscous shampoo which foams well and permits ready combing of the hair.

Example 9 There are mixed:

Fatty alcohol (c -c condensed with 12 mol. of ethylene oxide 12 g. Disodium salt of N -[alkyl(copra)aspartyl]- N [alkyl(copra)] N (N',N diethylaminopropyl)asparagine 6 g. Lactic acid to pH 5. Water to 100 cc.

Octylphenol condensed with 15 mol. of ethylene oxide 8 g. Diethanolamide of fatty acids of copra 2 g. Disodium salt of N -[alkyl(copra)aspartyl1- N [alkyl(tallow)] N (N,N diethylaminopropyl) asparagine g. Lactic acid to pH 7. Water to 100 cc.

An oily shampoo is obtained which leaves the hair soft and silky. In addition, no accumulation of electricity occurs on the hair.

Disodium salt of N -[alkyl(copra)aspartyl]- N [alkyl(c-opra)] N (N,N dimethylaminopropyl)asparagine 6 g. Lactic acid to pH 3. Water to cc. This shampoo, which is of oily appearance, makes the hair easy to comb and renders it soft and silky.

Example 12 There are mixed: Lauryl alcohol condensed with 15 mol. of ethylene oxide 8 g. Diethanolamide of copra fatty acids 2 g. Disodium salt of N [a1kyl(c0pra) aspartyl] N -[alkyl(copra)] N (N,N dimethylaminopropyl)asparagine 5 g. Lactic acid to pH 8. Water to 100 cc. This shampoo, which has an oily consistency, leaves the hair soft and supple. It exhibits no accumulation of electrostatic charges after drying.

Example 13 There are mixed:

Sulphate of C C alcohols and of ammonium (expressed as active constituents) 9 g. Disodium salt of N -[alkyl(copra)aspartyl1- N [alkyl(copra)] N (N,N diethylaminopropyl)asparagine 1g. Lactic acid to pH 6.8. Water to 100 cc.

This shampoo imparts softness to the hair and avoids the accumulation of electrostatic charges.

What is claimed is: 1. A compound of the formula RNH(|JHCH2C O-N-OHCHZC O-NH-(OHz) ..-N

COOH Ra GOOH R2 or their acid addition and sodium, potassium and ammonium salts, in which R1I TRz is selected from the group consisting of dilower alkylamino, morpholino or piperidino, wherein n is 2 to 5, and at least one of R and R are alkyl radicals of 10 to 18 carbon atoms.

2. A compound as claimed in claim 1 in which n is 2. 3. A compound as claimed in claim 1 in which n is 3. 4. A compound as claimed in claim 1 in which R and R are methyl.

5. A compound as claimed in claim 1 in which R and R are ethyl. 6. A compound as claimed in claim 1 in which I R N-Ra is morpholino.

7. A compound as claimed in claim 1 in which R and R are alkyl radicals derived from copra fatty acids.

8. A compound as claimed in claim 1 in which R and R are alkyl radicals derived from tallow fatty acids.

9. A compound of the formula OzHs OHZ C ONH (clam-N RaNCHCOONa -OHa-0H-000Na in which R and R are alkyl radicals derived from copra.

10. A compound of the formula in which R and R are alkyl radicals derived from copra.

11. A compound of the formula in which R and R are alkyl radicals derived from copra.

12. A compound of the formula in which R and R are alkyl radicals derived from tallow.

10 13. A compound of the formula CzH5 0H,0 O-NH (emu-N R3NOH-C 0 ONa 02m in which R and R are alkyl radicals derived from tallow.

14. A compound of the formula acid and R is an alkyl radical derived from copra fatty acid.

15. A compound of the formula OHg-CH2 0112-0 O-NH (0 H2) g-N 0 Ra-N0 H-0 0 OK CHz-Ofi:

in which R and R are alkyl radicals derived from copra fatty acid.

References Cited UNITED STATES PATENTS 1/1958 Price 260534 11/1964 Kezerian et a1. 260534 ALEX MAZEL, Primary Examiner. J. TOVAR, Assistant Examiner. 

1. A COMPOUND OF THE FORMULA
 15. A COMPOUND OF THE FORMULA 